Na1.614Li0.386Ti6O13 Single crystal was synthesized by a Li+ ion-exchange method from Na2Ti6O13 single crystal in a molten salt of LiNO3. The obtained Na1.614Li0.386Ti6O13 single-crystal is colorless and has the shape of a rod. Na1.614Li0.386Ti6O13 crystallizes in the monoclinic tunnel type structure, space group C2/m, and lattice parameters a = 15.144(2) Å, b = 3.7492(5) Å, c = 9.162(2) Å and β = 99.0131(9)º. The structure was determined by a single-crystal X-ray study and refined to the conventional values of R = 0.0247 and wR = 0.0451 for 969 independent observed reflections.